Method of coating leather with polymers containing morpholino groups and the resulting article



nite States ar METHGD F COATING LEATHER WITH POI- MERS CGNTAINHQG RHBRPHGLWO GRQUPS AND THE RESULTING ARTICLE Paul W. McWherter, Philadelphia, Benjamin B. Kine,

Levittowu, and Hugo A. Alps, Philadelphia, P3,, assignors to Rohm & Haas Company, Philadelphia, Pa, a corporation of Delaware No Drawing. Application March 21, 1955 Serial No. 495,807

17 Claims. (Cl. 117-76) leather and to each other and excellent softness and flexibility even under extremes of cold and heat.

U. S. Patent 2,204,520 discloses a procedure for applying aqueous dispersions of emulsion-polymerized acrylic acid esters or the like to leathers. Such dispersions in practice are frequently provided with pigments and are generally covered with one or more final lacquer top coats. The aqueous dispersion serves to fill imperfections and to level the surface of the leather and to improve the adhesion between any lacquer top coats applied and the leather. The coatings obtained from the aqueous dispersions disclosed in the patent provide good adhesion to many leathers and particularly to snuffed, buffed and split leathers. However, on some types of full grain leathers such coatings have poor adhesion. This poor adhesion is particularly noticeable on leathers which have been-subjected to certain types of fat-liquoring, such as sperm oil, or which have acquired such a large amount of fatty deposits on the surface of the leather during fatliquoring as to in effect provide a resist to aqueous coating compositions.

It has now been discovered that improved adhesion may be obtained between the leather and polymers applied to it by means of an aqueous vehicle if the polymer contains mo1pholino groups. In accordance with the present invention, it has been found that the application of aqueous dispersions of certain resins containing morpholino groups to the leather provides improved adhes-ion to full grain leathers as well as to buffed and split leathers and also improves the resistance to scufling resulting from rubbing action against the finished leather surface as well as improvement in resistance to wet molding operations.

To impart the improved qualities in the finished leathers in accordance with the present invention, the leather is coated with an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomeric compound having the structure of the general formula I following:

CHFCHQAN 0 6-0 Ha Ha where A is a straight or branched chain alkylene group having 2 to 10 carbon atoms, preferably 2 to 3 carbon atoms.

These compounds may be referred to as morpholinoalkyl vinyl ethers or as N-vinyloxyalkylmorpholines.

The polymers must not be water-soluble. Where the morpholino-containing monomer that is polymerized is ice of such character that a homopolymer produced therefrom is appreciably water-soluble, it is necessary to copolymerize such a monomer with at least one other copolymerizable monoethylenically unsaturated monomer which is of a character that will render the final copolymer insoluble in water. Many of the morpholino-containing monomers have such a large proportion of hydrophobic groups in their molecule that homopolymers thereof will necessarily be water-insoluble and, in such cases, a homopolymer can be applied to the leather for accomplishing the purpose of the invention. Frequently, however, it is preferable from the cost standpoint, and for controlling properties, such as flexibility, to copolymerize the morpholino monomer with 50% or more of one or more less expensive and more readily available comonomers. Preferred compositions of the invention are, therefore, those copolymers of from 5% to 15% of the morpholino-containing monomer or of :a mixture of such monomers, the balance of the copolymer being formed of other less expensive comonomers.

Other polymerizable compounds containing a single ethylenically unsaturated group that may be copolymerized with the morpholino-containing monomer to produce binary, ternary, etc. copolymers include the esters of acrylic acid or methacrylic acid or the dimer of methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl, phenylethyl, and the like; diesters of itaconic acid and the above alcohols; esters of maleic, fumaric, or citraco-nic acids with the above alcohols; vinyl esters of carboxylic acids such as acetic, propionic, butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.; vinyl ethers and sulfides such as ethyl vinyl ether, ethyl vinyl sulfide, butyl vinyl ether, octyl vinyl ether; methacrylonitrile or acrylonitrile; acrylamide, or methacrylamide, and N-alkyl-substituted amides of these types; vinyl toluene, vinyl naphthalenes,

' such as 4-chloro-l-vinyl naphthalene, and styrene.

The emulsifiers or dispersing agents that may be used for preparing the monomeric emulsions before copolymerization ordispersions of the polymer after poly-- merization may be of anionic, cationic, or non-ionic type or a mixture of two types may be used.

Suitable anionic dispersing agents include the higher fatty alcohol sulfates, such as sodium lauryl sulfate, alkylaryl sulfonates, e. g. sodium or potassium isopropylbenzene sulfonatcs or isopropyl naphthalene sulfonates, alkali metal higher alkyl sulfosuccinates, e. g. sodium octyl sulfosuccinate, sodium N-methyl-N-palmitoyltaurate, sodium oleyl isothionate, alkali metal salts of alkylarylpolyethoxyethanol sulfates or sulfonates, e. g. sodium t-octylphenoxypolyethoxyethyl sulfate having 1 to 5 oxyethylene units.

' Suitable cationic dispersing agents include lauryl pyridinium chlorides, cetyl dimethyl amine acetate, and alkyldimethylbenzylammonium chlorides in which the alkyl group has from 8 to 18 carbon atoms, such as octyl, decyl, dodecyl or octadecyl, t-octylphenoxyethoxyethoxydimethylbenzylammonium chloride.

Suitable non-ionic dispersing agents includethe following: alkylphenoxypolyethoxyethanols having alkyl groups of about seven to eighteen carbon atoms and 6 to 60 or more oxyethylene units, such as heptylphenoxyp o l y e t h o x y e t h a n o l s, octylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, dodecylphenoxypolyethoxyethanols, and the like; polyethoxyethanol derivatives. of methylene linked alkyl phenols; sulfur-containing agents such asthose made by condensing 6 to 60 or more moles of ethylene oxide with nonyl, dodecyl, tetradecyl, t-dodecyl, and the likemercaptans or with alkylthiophenols 3 having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, such as lauric, myristic, palmitic, oleic, and the like or mixtures-of acids such as found in tall oil containing 6 to 60 oxyethylene units per molecule; analogous ethylene oxide condensates of long-chained alcohols, such as octyl, decyl, lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrophobic hydrocarbon chain, such as sorbitan monostearate containing 6 to 60 oxyethylene units, etc.; also ethylene oxide condensates of long-chain or branched chain amines, such as dodecylamine, hexadecylamine, and octadecylamine, containing 6 to 60 oxyethylene groups; block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxid sections.

Particularly valuable resin dispersions are obtained by emulsifying a mixture of (a) one or more of the morpholino containing monomers above and (b) one or more monomeric esters of acrylic, methacrylic, or itaconic acid or mixtures of these acids in water and polymerizing the mixture while it is in the emulsified form. The monomeric esters which have proven to be most satisfactory are the alkyl esters in which the alkyl group contains one.

to eight carbon atoms and which are exemplified by the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, and 2-ethylhexyl acrylates, methacrylates, and itaconates.

The polymerizable emulsions can be prepared at temperatures from C. to about 100 C,, but intermediate temperatures are much preferred. Thus, when the preferred copolymers with esters are made with the esters in which the alkyl group contains one to four carbon atoms a temperature from about C. to about 60 C. is employed whereas a higher temperature; e. g., 30 C. to 80 C., is recommended when esters containing five to eight carbon atoms in the alkyl group are copolymerized. Peroxidic free-radical catalysts, particularly catalytic systems of the redox type, are recommended. Such systems, as is well known, are combinations of oxidizing agents and reducing agents such as a combination of potassium persulfate and sodium metabisulfite. Other suitable peroxidic agents include the per-salts such as the alkali metal and ammonium persulfates and perborates, hydrogen peroxide, organic hydroperoxides such as tertbutylhydroperoxide and cumene hydroperoxide, and esters such as tert-butyl perbenzoate. Other reducing agents include water-soluble thiosulfates, hydrosulfites, tertiary amines, such as triethanolamine, thiourea, and the salts, such as the sulfates, of metals which are capable of existing in more than one valence state such as cobalt.

agitating an aqueous suspension or emulsion of the mix ture of copolymerizable monomers and a redox catalytic combination at roomtemperature without the application of external heat. The amount of catalyst can vary but for purposes of efficiency from 0.01% to. 3.0%, based on the weight of the monomers, of the peroxidic agent and the same or lower proportions of the reducing agent are recommended-. In this way, it is possible to prepare dispersions which contain as little as 1% and as much as 60% or even more of the resinous copolymer on a weight basis. -It is, however, more practical, and hence preferred, to produce dispersions which contain about 30% to-50% resin-solids. Preferably a pigment is introduced into the aqueous coating dispersion and the amount of pigment introduced dispersing agents mentioned above may be used. In addition, a small amount of a protective colloid may be included to thicken and/ or stabilize the suspension and prevent the pigment from settling out. Examples of such colloids include methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, sodium, potassium, or ammonium alginates, ammonium or alkali metal salts of homopolymers and copolymers of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like, such as ammonium polyacrylate, ammonium salts of copolymers of styrene and maleic acid, sodium methacrylate, and so on.

The aqueous dispersion of the polymer or copolymer with or without a pigment'dispersed or suspended therein may be applied to the leather at a solids concentration of 10% to 50% (including the weight of polymer and pigment, if any). It may be applied by any suitable equipment such as by brushing, swabbing, or spraying on to the leather. After application of the dispersion, it

. may be dried on the leather either by drying in the ammay vary from that equivalent to about 10% to 150%' V by weightof the polymer. Generally, the pigment is first dispersed in water (to a concentration of about 30% to 45%) by means of a non-ionic or anionic dispersing agent or a mixture of both types. thereof. Any o bient atmosphere or at somewhat elevated temperatures up to 50 C- The amount of copolymer applied on the leather varies widely with the type of leather and the ultimate finish desired. For most purposes, the amount applied per thousand square foot of the leather may vary from 1 to 15 pounds.

It is believed that the improved adhesion obtained on leather by the application of the polymers containing the morpholino groups is attributable to some chemical or physicochemical reaction between such groups and the protein molecules of the leather or with the tanning agent or fatliquor deposit on the leather, or possibly on some joint reaction with two or more of these substances.

However, it is not intended that the invention be limited by any particular theory of operation.

. For some purposes, the leather product carrying the single coating obtained from the application of the aqucous dispersion of the polymer containing morpholino groups. with or without pigment may serve as suitable finished product. For example, thismay be the case when it is desired only to impart a water-repellent surface to the leather and the polymer applied by the aqueous dispersion is of highly hydrophobic character either as the result of the presence of a long-chain hydrocarbon group in the morpholino-containing monomer or as the result of such a long-chain hydrocarbon group in the comonorner or as a result of long-chain hydrocarbon groups in bo h of such monomers. However, in many cases, it may be desired to apply one or more additional coatings of a lacquer type over the coating obtained from the a .is polymer dispersion. Any suitable lacquer composition may be ap plied suchas those which comprise :as the film-forming materialan addition polymer of vinyl, acrylic or related types, a cellulose derivative such as a nitrocellulose or cellulose organic acid esters such as cellulose acetate, cellulose acetate butyrat e or the like. The lacquers may com-prise a plasticizer'if the film-forming agent itself is not adequately flexible. When a single lacquer top coat ing isapplied over the coating obtained from the aqueous polymer dispersion, it may be clear, it may be dulled by a filler or other suitable agent, such as a water-insoluble soap, like aluminum stea'rate or silicas, or it may be colored with a suitably colored pigment. Preferably at least two lacquer top coatings are applied in succession over the coating obtained from the aqueous dispersion. When two such lacquer coatings are applied, the first is preferably pigmented to augment the color and covering obtained by the pigment, if any, applied by the coating from the aqueous dispersion and the second lacquer coating is preferably clear or merely dulled to provide the glossiness or flatness desired in the final surface.

7 Each of the, subsequently applied coatings should be dried before .any later coating is to be applied and drying may be effected as before either at normal room temperature in the ambient atmosphere or at somewhat elevated temperatures up to 50C.

If desired, the leather may be embossed after the coating applied in the aqueous dispersion has been dried on the leather and before subsequent lacquer coatings are applied, or embossing may be applied at any time after subsequent coatings are applied but preferably before the last or final coat is applied. Such embossing should, in all cases, be applied to the coated leather in a dry condition.

As the vinyl or acrylic addition polymer that may be used for the film-forming component of the subsequently applied lacquer or lacquers, there may be used one or more homcpolymers or copolymers of the following monoethylenically unsaturated compounds: vinyl chloride, vinyl acetate, vinyl propionate, vinylidene chloride, esters and nitriles of acrylic and methacrylic acids such as acrylonitrile, methacrylonitrile, and the alkyl esters of acrylic or methacrylic acid in which the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, hexadecyl and octadecyl. Besides the above homopolymers and copolymers, polyvinyl metals such as polyvinyl acetal itself, polyvinyl butyral or partially hydrolyzed homopolymers and copolymers of Vinyl ace tate, vinyl propionate or of acrylic and methacrylic esters may be used. Such compounds contain reactive hydroxyl and carboxyl groups. Other polymers containing reactive groups may be used provided the polymers do not contain sufiicient reactive groups to render them insoluble in the organic solvent employed. Such polymers include the copolymers containing up to 50 mole percent of hydroxyethyl vinyl ether or of ,6 hydroxypentyl vinyl ether, up to 50 mole percent of aminoethyl acrylate, aminoethyl vinyl ether or N-methylor N- ethylaminoethyl vinyl ether, or up to 30 mole percent of a vinyl pyridine, such as 2-vinyl pyridine or 4-vinyl pyridine, or of an amide, such as acrylamide, methacrylamide, N-methyl acrylamide, or of an acid, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and the dimer or trimer of methacrylic acid, or the like. I

When a plasticizer is used, it may be a polyester, polyamide, or polyester amide such as may be obtained by the condensation reaction of a dibasic acid with a polyol or a polyamine. More particularly, the plasticizer (which may be termed a polymeric plasticizer) may be obtained by reacting combinations of materials of the general types noted below:

I. Glycols (or other polyols) and dibasic acids 11. Amino alcohols and dibasic acids III. Glycols, diamines and dibasic acids 1V. Glycols, amino alcohols and dibasic acids V. Amino alcohols, diamines and dibasic acids Vi Amino acids, glycols and d-ibasic acids VII. Amino acids, amino alcohols and dibasic acids Vlll. Amino alcohols, glycols and dibasic acids EX. Amino alcohols, dibasic acids and hydroxycarboxylic acids. 1

It isadvantageous to use a smail excess of the alcoholichydroXyl-containing constituent in preparing the polymers.

Examples of polyols include itrimethylol methane and erythritol. Examples of glycols are ethylene glycol, propylene glycol, diethylene glycol, trirnethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, ltl2-octadecanediol and pentaglycol.

Examples of dibasic carboxylic acids are malonic, succinic, glutaric, adipic, ,8-rnetl1yladipic, pimelic, suberic, azelaic, sebacic, undecanedioic, brassylic, isophthalic, hexahydroterephthalic, p-phenylene-diacetic and acetonedicarboxylic acid.

Any amino alcohol having at least one hydrogen atom attached to the amino nitrogen atom may be employed including aromatic amino alcohols, e. g. p-hydroxymethylbenzylamine, 4-hydroxymethyl 4 aminomethyldiphenyl and p-aminophenylethyl alcohols; aliphatic amino alcohols, e. g. .5 aminopentanol-l:6-amino-5-methylhexanol 1,4(p aminophenyDcyclohexanol, hydroxyethoxyethoxyethylamine, and N (B aminoethyl) N- omega-hydroxyhexyl) -aniline.

The preferred amino alcohols are of formula Where R represents saturated divalent hydrocarbon radicals with a chain length of at least two carbon atoms. Amino alcohols which fall within this group include ethanolamine, 3-aminopropanol, 4-aminobutanol, 6- aminohexanol, and IO-aminodecanol.

Any diamine may be employed, which contains at least one hydrogen atomattached to each amino nitrogen atom. The preferred diamines are of formula where R represents saturated divalent hydrocarbon radicals with a chain length of at least two carbon atoms, e. g. ethylenediamine, hexamethylenediamine, S-methylhexamethylenediamine, and decamethylenediamine. However, aromatic diamines such as m-phenylenediamine may also be used.

Any polymerizable monohydroxy monocarboxyli-c acid or ester-forming derivative thereof may be employed. The preferred hydrox acids are of formula where R represents saturated divalent hydrocarbon radicals, e. g. o-hydroxycaproic, IO-hydroxydecanoic, and l2-hydroxystearic acid.

Any polymeriza-ole monoaminomonocarboxylic acid or ester-forming derivative thereof may be employed including 6-aminocaproic, 9-arninononanoic, and ll-amino undecanoic, and l2aminostearic acids, caprolactum, etc.

The organic solvents that may be used include ketones such as acetone, methyl ethyl ketone and dioXane; hydrocarbons such as xylene, toluene, benzene as well as parafiinic or naphthenic types such as solvent naphthas, esters such as ethyl, propyl, butyl and amyl acetate as Well as ethoxyethyl acetate, butoxyethyl acetate and the like, or ethers such as butyl ethyl ether. The solvent may comprise a mixture of several types. If a polyisocyan-ate is used as suggested hereinafter, a solvent should be of a type which does not contain an active hydrogen.

The pigments that may be employed in the lacquers or the aqueous copolymer dispersion or in both of these media include red iron oxide, chrome green, molybdate chrome orange, phthalocyanines, such as copper phthalocyanine, titanium dioxide, lithopone, chrome yellow, ultramarine blue, red cadmium, yellow cadmium, organic toners and lakes, and so on.

It has been found that the adhesion between the leather and the coating thereon, especially when several layers are applied to the leather, is even further improved when a polyisocyanate is applied to the coated leather at any time after the aqueous polymer dispersion has been dried on the leather. For example, the polyisocyanate may be applied by spraying or swaobing over the dried polymer coating obtained from the aqueous dispersion. It may also be applied as a component in any of the subsequently applied lacquers or it may be applied to the dried coated leather after any of the subsequently applied lacquers. Preferably, if a polyisocyanate is employed, it is incorporated in the first lacquer coating applied over the polymer coating obtained from the aqueous dispersion.

Examples of the polyisocyanates that may be employed include especially the hydrocarbon polyisocynates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, p-phenylene diisocyanate, mphenylene diisocyanate, naphthalene diisocyanates, benzene 1:3:5 triisocyanate, toluene-2:4:6-triisocyanate, ethylbenzene-2:4:6 triisocyanate, monochlorobenzene- 2:416 triisocyanate, triphenylmethane 4:4':4".-tri isocyanate and 'diphenyle2:4:4 -triisocyauate, toluene-2,4- diisocyanate, 4,4'-diisocyanato-biphenyl, 3,3-dimethyl- 4,4-diisocyanato-biphenyl, and 3,3'- dimethoxy 4,4-diisocyanatobiphenyl. The polyisocyanates have various reactivities, some being much slower than others. For example, diphenylmethane-4,4-diisocyanate is highly reactive whereas the 3,3-dimethoxy-4,4-diis-ocyanato-biphenyl is relatively slow. To compensate for the difference in reactivity, the proportion added may be increased for the slower ones and decreased .for the faster ones or basic catalysts, such as tertiary amines may be included, especially with the slower ones. Mixtures of the polyisocyanates may be used of which preferred combinations are mixtures of toluene-2,4-diisocyanate with either 3,3-dimethyl-4,4' diisocyanato-biphenyl or 3,3'-dimethoxy-4,4'-diisocyanato-biphenyl.

When one or more lacquer coatings are to be applied after the application of the polyisocyanate, it is preferred that the drying of the polyisocyanate in place on the coated leather should not be so prolonged or at'such "high temperatures that all the isocyanate groups are com- .pletely reacted. By so leaving the active isocyanate groups the drying of subsequent lacquer coatings provides the opportunity for reactive combination of isocyanate groups with any reactive groups that may be present in such subsequently applied lacquers.

It appears that, when a polyisocyanate is used, the improved adhesion between the several layers of the coating and between the leather is at least partially attributable to some reaction between the polyisocyanate, the leather, the film-forming component and possibly the plasticizer in the several coatings. It should be understood, however, that the application to the leather of the aqueous dispersions of polymers containing morpholino groups as defined hereinabove imparts improved adhesion between lacquer coatings and the leather and shows improved adhesion between the leather and the polymer deposited from the aqueous dispersion. This adhesion is for most purposes fully adequate even without the employment of a polyisocyanate. The application of the polyisocyanate, however, may be desirable to obtain even better adhesion for some particular purposes and has also the advantages of increasing the dryness orslipperiness of the top surface of the coated leather. When two lacquer coats are applied over the coating obtained from the aqueous polymer dispersion, the first of such lacquers preferably has the following composition: from 20 to 200 parts by weight of plasticizer, if present, per 100 parts of the addition polymer or cellulose ester; from 5 to 150 parts by weight of a pigment or mixture of pigments per 100 parts of the film-forming component; from 1% to 65% by weight of a polyisocyanate, if used, this percentage being based on the sum of the weights of the plasticizer and film-forming component. The amount of solvent employed may be such as to provide a solids concentration (that is materials other than the solvent themselves) of 2% to 20% by weight. The final lacquer coat is usually an unpigmented solution (either clear or dulled by an inert delustering filler) of the plasticizer and film-forming component, either or both of which may be the same as or diiferent from the respective plasticizer and film-forming component of the first lacquer coat. 'When' both lacquer coats contain plasticizer, the proportion in the final coating is somewhat less in proportion to the film-forming component than the proportion used inthe first lacquer coating. Generally, it is within the proportion of 15 to 80 parts per 100 parts of the film-forming component.

In thefollowing examples, which are illustrative of the invention,parts and percentages are by weight unless otherwise specified:

' Example I (a) A dispersion of a copolymer was prepared by emulsifying 80 parts by weight of ethyl acrylate, l5 par-ts by weight of n-butyl acrylate and 5 parts by weight of morpholinoethyl vinyl ether in about 300 parts by weight of water with about 2 parts by weight of sodium lauryl sulfate and 6 parts by weight of an ethylene oxide condensation product of an octyl phenol containing between 30 and 50 oxyethylene units per molecule. To the emulsified monomers 0.3% by weight of ammonium persulfate, 0.06% of sodium hydrosulfite, and 1% triethanolamine were added to catalyze the copolymerization which was carried out for a period of about fifteen minutes during which the temperature rose from 20 C. to 45 C.

(-b) Nine parts of red iron oxide are dispersed in 14 parts of Water by means of two parts of a suitable dispersing agent, such as a mixture of equal parts of sodium lauryl sulfate and t-octylphenoxypolyethoxyethanol containing about 10 oxyethylene units in combination with z part of a suitable protective colloid, such as methyl cellulose, and the mixture was added to 100 parts of the copolymer dispersion of part a hereof. The resulting pigmented dispersion was swabbed on several pieces of a full grain upholstery leather and dried at 50 C. The coating exhibited excellent adhesion to the leather.

(c) The procedure of parts a and b hereof is repeated except the morpholinoethylvinyl ether is omitted so that a dispersion of a copolymer of ethyl acrylate and n-butyl acrylate is produced and applied to the full grain upholstery leather. The coating on the leather could be pulled off the leather intact.

Example 2 (a) A mixture of 40 parts of red iron oxide, six parts of a plasticizer consisting of a polyester obtained by the reaction of sebacic acid with an excess of propylene glycol and having a number average molecular weight of about 4,000, 2.9 parts by Weight of a copolymer of 90% vinyl chloride and 10% vinyl acetate having a number average molecular weight of about 40,000, 6.1 parts ethoxyethyl acetate, 25 parts of methyl ethyl ketone and 20 parts of a petroleum solvent consisting of a mixture of aromatic, naphthenic, and aliphatic hydrocarbons is ground in a ball mill for 24 hours to form a pigment dispersion.

(b) A solution is also formed from 3.1 parts of the same plasticizer as above and 5.0 parts of the same vinyl copolymer in 10 parts of ethoxyethyl acetate, 44 parts of methyl ethyl ketone and 34.9 parts of a hydrocarbon solvent largely consisting of xylol.

(c) The solution of part [2 hereof is then mixed with the milled pigment dispersion of part a hereof in the ratio of 90 parts of the former to 10 parts of the latter.

The resulting dispersion is applied to apiece of the coated leather obtained in part b of Example 1 and dried at 50 C. for about three hours.

(d) Then a clear coating is applied to the coated leather obtained in part 0 hereof by spraying a solution containing about 1.5% of the same plasticizer (of part a a) and'5% of the same vinyl copolymer (of part a) in a solvent mixture composed of 10% of ethoxyethyl acetate, 55% methyl ethyl ketone and 35% of a hydrocarb on composed largely of xylene. After applying the clear coating by spraying, it was dried at 50 C. The final coated leather had'a glossy color and was soft and flexible.

Example 3 (a) The procedure of Example 2, parts a through d is repeated except that 3.0 parts of toluene-2,4-diisocyanate is added to the solution of part b thereof. The

diisocyanatein part. b. ofExample .1.

(b) The procedure of Example 2, parts a through d,

linopropyl vinyl ether.

9 is repeated except that 3.0 parts of toluene-2,4-diisocyanate is added to the solution of part b thereof and the dispersion obtained in part c thereof is applied to the leather obtained in part c of Example 1 wherein the full grain upholstery leather is coated with a copolymer of ethyl acrylate with butyl acrylate. The adhesion of the coatings to the leather is fair but special precautions are needed during wet molding operations to prevent damage to the finished leather.

Example 4 Example 5 (a) A dispersion containing 15% of a copolymer of 75% ethyl acryl-ate, 15% n-butyl acrylate and morpholinoethyl vinyl ether is pigmented as in Example 1(b), applied to a full grain leather, and dried as in Example l(b). Good adhesion between the coating and the leather is obtained.

(12) The coated leather is top coated as in parts a through d of Example 2. The coated leather shows good adhesion between the lacquer coating and the leather.

Example 6 (a) An aqueous dispersion containing 20% of a copolymer of 35 parts by weight of ethyl methacrylate, 50 parts by weight of Z-ethylhexyl acrylate and parts by weight of morpholinoethyl vinyl ether is pigmented as in Example 1(b) except the red iron oxide is replaced with molybdate chrome orange. After application to the leather and drying as in Example 1*(b), the coating shows good adhesion to the leather.

(b) The coated leather of part a hereof is top-coated as in Example 2, parts a through d except that the red iron oxide is replaced with molybdate chrome orange. The coated leather exhibited good adhesion between the lacquer coatings and the leather.

Example 7 An aqueous dispersion containing by weight of a copolymer of 92 parts by weight of propyl acrylate, 5 parts by weight of acrylonitrile, and 3 parts by weight of morpholinoethyl vinyl ether is applied to a full grain leather in the manner described under Example 1, parts a and b after pigmenting according to that procedure.

The application of an aqueous dispersion of a polymer to a leather for the purpose of coating it avoids excessive impregnation of the leather which sometimes occurs when a polymer is applied from an organic solvent solution thereof. It, therefore, avoids the stiffening and the undesirable break and feel of the coated product that are caused by severe impregnation. At the same time, the application of the aqueous dispersion of the polymer has the advantage of enabling the operator to apply the composition containing a large proportion of solids therein without encountering the disadvantages of high viscosity and low mobility which would be encountered if the polymer were applied by the use of an organic solvent solution. In addition, the application of the particular polymers of the present invention by an aqueous dispersion provides improved adhesion for many types of leather, particularly those which have a large amount of fatty deposits on the surface of the leather as a result of the fatliquoring operations. When lacquer top coatings are applied over the coating applied from the aqueous dispersion of the particular polymers of the invention, improved adhesion is obtained between the lacquer top coating system and the leather as compared to that obtained with polymers heretofore suggested to be applied by aqueous dispersion which contain no morpholino groups.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomeric compound having the structure of the formula I H2 H2 OHz=CHOAN CO H1 H2 where A is an alkylene group having 2 to 10 carbon atoms.

2. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of morpholinoethyl vinyl ether.

3. As an article of manufacture, a leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of morpholinopropyl vinyl ether.

4. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomeric compound having the structure of Formula I as defined in claim 1 and, superimposed on said layer, at least one lacquer coating compriting a film-forming component.

5. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of morpholinoethyl vinyl ether, and, superimposed on said layer, two lacquer coatings the first of which is pigmented.

6. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about 5% to 15% by weight of a compound having the structure of Formula I as defined in claim 1, and, superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

7. As an article of manufacture, a leather having multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about'5% to 15% by weight of morpholinoethyl vinyl ether, and. superimposed on said layer, a pigmented laccuer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

8. As an article of manufacture, a leather having a multi-layer coating thereon, one layer f which comprises a pigmented water-insoluble linear polymer of about to 15% by weight of morpholinopropyl vinyl ether, andv superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

9. As an article of manufacture, a leather having a multi-layer coating thereon, one layer of which comprises a pigmented water-insoluble linear polymer of about by weight of ethyl acrylate, 15% by weight of n-butyl acrylate and 5% by weight of morpholinoethyl vinyl ether, and, superimposed on said layer, a pigmented lacquer coating comprising a vinyl resin and a plasticizer for the vinyl resin.

10. Them'ethod of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of monoethylenically unsaturated mole culcs comprising at least 3% by weight of a monomeric compound having the structure of Formulal as defined in claim 1, and then drying the coated leather.

11. The method of finishing leather comprising applying thereto an aqueous dispersion of a water-insoluble linear polymer of at least 3% by weight of morpholinoethyl vinyl ether, and then drying the coated leather.

7 12. The method of finishing leather comprising applying thereto an aqueous dispersion of a Water-insoluble linear polymer of at least 3% by weight of morpholinopropyl vinyl ether, and then drying the coated leather.

13. The method of finishing leather comprising applying thereto an aqueous dispersion of a Water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by Weight of a monomeric compound having the structure of Formula I as defined in claim 1, then drying the coated leather, applying thereto a lacquer, at least one of said dispersion and lacquer being pigmented, and drying the lacquer.

14. As an article of manufactue, a full-grain leather having a coating thereon comprising a water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomeric compound having the structure of Formula I as defined in claim 1.

15. As an article of manufacture, a full-grain leather having a coating thereon comprising a water-insoluble 30 linear polymer of monoethylenically unsaturated molecules comprising about 5% to 715% by weight of a monomeric compound having thestructure of Formula I as defined in claim 1. i

' 16,. As an article of manufacture, a full-grain leather having a multilayer coating thereon, one layer of which comprises a pigmented Water-insoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by Weight of a monomeric compound having the structure of Formula I as defined in claim 1, and, superimposed on said layer, at least one lacquer coating comprising a film-forming component.

'17. The method of finishing full-grain leather comprising applying thereto an aqueous dispersion of a'waterinsoluble linear polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomeric compound having the structure of Formula I as defined in claim 1, and they drying the coated leather.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,031 Graves Nov. 29, 1938 2,138,763 Graves Nov. 29, 1938 2,204,520 Walker et a1. June 11, 1940 2,374,678 Gruenwald May 1, 1945 2,430,479 Prattet a1. Nov. 11, 1947 2,601,251 Bruson June 24, 1952 2,694,688 Hughes Nov. 16, 1954 FOREIGN PATENTS 7 475,131 GreatBritain Nov. 15, 1937 

1. AS AN ARTICLE OF MANUFACTURE, A LEATHER HAVING A COATING THEREON COMPRISING A WATER-INSOLUBLE LINEAR POLYMER OF MONOETHYLENICALLY UNSATURATED MOLECULES COMPRISING AT LEAST 3% BY WEIGHT OF A MONOMERIC COMPOUND HAVING THE STRUCTURE OF THE FORMULA 